Cage‐Confined CuO Nanoparticles: Unlocking Site‐Selective Catalysis for Borylation of α,β‐Unsaturated Conjugated Compounds

Small Methods, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Abstract The borylation of α,β‐unsaturated carbonyl compounds is pivotal for constructing multifunctional organoboron intermediates in pharmaceuticals and materials. Here, the study reports CuO@COP1‐T, a novel catalyst integrating CuO nanoparticles (NPs) within covalent organic porous cage (COP1‐T), which achieves unprecedented site‐selectivity conjugated compounds. Experimental results demonstrate CuO@COP1‐T exhibits 100% monoboration selectivity trans‐dibenzylideneacetone, surpassing unsupported CuO@NPs (8%). Molecular dynamics (MD) simulations reveal 1.2 nm triangular pores enforce via geometric matching with reaction intermediates. Optimization conditions clarifies impacts methanol amount, solvent type, base addition. retains >95% activity over five cycles, showcasing robust stability. This work establishes synergistic platform where COP1‐T stabilizes NPs while creating confined microenvironment to spatial confinement effects, providing rational design strategy confined‐metal catalysts chemistry.

Language: Английский

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N-Triflylation Enables δ-Valerolactam-Epoxide Alternating Copolymerization

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 597 - 602

Published: April 27, 2025

δ-Valerolactam (VL), a six-membered cyclic amide, is easily accessible but hardly polymerizable, unlike other-membered homologues. We have discovered that simple N-triflylation effectively activates VL for undergoing copolymerization with epoxides. The strong electron-withdrawing triflyl group allows mild organobases, in cooperation triethyl borane and an alcohol initiator, to trigger the reaction at room temperature, affording strictly alternating poly(ester-sulfonamide) controlled molar mass low dispersity. method proven applicable variety of epoxides, regardless polarity bulkiness substituents, products exhibit good chemical degradability, thermal/enzymatic stability, wide range glass transition temperatures. study indicates N-sulfonylation ring-opening (alternating) together may build up versatile platform support design construction heteroatom-rich polymers using conventionally nonpolymerizable compounds.

Language: Английский

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Boron Compounds as Key Drivers of Innovation: Exploring Their Role in Environmental Remediation, Sustainable Agriculture, Advanced Biomedical Applications, and Green Chemistry

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 123688 - 123688

Published: April 1, 2025

Language: Английский

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Protein desulfurization and deselenization

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8521 - 8545

Published: Jan. 1, 2024

Methods enabling the dechalcogenation of thiols or selenols have been investigated and developed for a long time in fields research as diverse study prebiotic chemistry, engineering fuel processing techniques, biomolecule structures function chemical synthesis biomolecules. The thiol selenol amino acids is nowadays particularly flourishing area being pillar modern protein synthesis, when used combination with selenol-based chemoselective peptide ligation chemistries. This review offers comprehensive scholarly overview field, emphasizing emerging trends providing detailed critical mechanistic discussion methods so far. Taking advantage recently published reports, it also clarifies some unexpected desulfurization reactions that were observed past which no explanation was provided at time. Additionally, includes on principal within framework newly introduced green chemistry metrics toolkits, well-rounded exploration subject.

Language: Английский

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The green and efficient formation of the commercial cyclic carbonates from CO2 and epoxides promoted by metal-free quaternary phosphonium-boron catalysts and DMAP

Inorganica Chimica Acta, Journal Year: 2024, Volume and Issue: unknown, P. 122503 - 122503

Published: Dec. 1, 2024

Language: Английский

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Three-arms PLA/PS copolymer based on 2,5-dihydroxy-1,4-benzoquinone

Journal of Polymer Research, Journal Year: 2024, Volume and Issue: 31(7)

Published: June 18, 2024

Language: Английский

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2,6-Bis(pyrazol-1-yl)pyridine cobalt-catalyzed high selective hydroboration of alkenes

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 568, P. 114516 - 114516

Published: Sept. 1, 2024

Language: Английский

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Simple/commercially‐available Lewis acid in anionic ring‐opening polymerization: powerful compounds with multiple applications in macromolecular engineering

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 25, 2024

Abstract Simple and commercially available Lewis acids (LAs) are commonly used catalysts in anionic ring‐opening polymerization (AROP) reactions. In particular, for the AROP of epoxides, addition a acid allows transition from so‐called end‐chain mechanism to monomer‐activated mechanism. The presence LA simultaneously leads decrease reactivity active centers through formation three‐species ate complex activation monomer by coordination oxygen atom oxirane ring. These two effects result both an increase propagation kinetics transfer reactions, which has enabled synthesis high molecular weight polyethers. However, impact goes far beyond these classic effects. They have indeed new functional monomers as well heterotelechelic macromolecules. Also widely copolymerization reactions (statistical, sequential, alternating) can strongly influence composition sequence units Finally, also significantly architecture obtained This review aims list various contributions macromolecular engineering illustrate them with well‐chosen examples.

Language: Английский

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Fast Gelation and Mechanical Reinforcement of Tetrahydroxydiboron-Induced Free Radical Polymerized Hydrogels under Harsh Conditions

Macromolecules, Journal Year: 2024, Volume and Issue: 57(21), P. 9965 - 9976

Published: Oct. 18, 2024

Hydrogels prepared through free radical polymerization hold great promise for large-scale production and practical applications but face challenges due to oxygen inhibition during poor mechanical properties. These issues often necessitate complex structural designs time-consuming anaerobic processes. This work presents a novel approach using tetrahydroxydiboron (THDB) combined with potassium persulfate (KPS) rapidly produce hydrogels enhanced properties under aerobic conditions, overcoming traditional limitations. The THDB-KPS system facilitates the gelation of acrylamide (AM) precursors in just 2 min ambient significantly outperforming existing systems. method is versatile across various monomer types, including hydrophilic, electrolyte, macromolecular zwitterionic monomers. rapid effect stems from THDB's ability interact dissolved neutralize inhibitory effects oxygen, promote decomposition efficiently by homolytic cleavage (HO)2B· radicals coordination N or O vinyl monomers diboron structure. Meanwhile, boron-induced hydrogen bonding interactions, along fast rise temperature viscosity reaction system, contribute shortened time as well. factors also lead formation multiple physical cross-links well network densely loosely cross-linked regions. Consequently, hydrogel are progressive deformation these regions breakage cross-links. reinforcement remains effective even challenging acidic alkaline environments, low temperatures impurity-laden environments. Therefore, this breakthrough offers scalable efficient producing high-performance harsh promising substantial advancements industrial use diverse fields.

Language: Английский

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Regioselective Copolymerization of Glucose-Derived Allopyranoside Epoxide with Cyclic Anhydrides: Developing Precise Sugar-Functionalized Polyesters with Unique Altrose Linkages

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

Uniform sugar-functionalized polyesters combine the benefits of sugar's structural diversity, biocompatibility, and biodegradability with precise postfunctionalization capabilities, making them a highly valuable class materials extensive application potential. However, irregular placement hydroxyl groups has limited synthesis these polyesters. Here, we present first platform for uniform via regioselective ring-opening copolymerizations (ROCOPs) allopyranoside anhydrosugar epoxide (

Language: Английский

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